将单一硫脲同时作为硫源和氮源,三嵌段共聚物表面活性剂F127聚醚作为软模板剂,利用水热法合成了氮/硫共掺杂介孔碳复合材料。结果表明,合成的复合材料中硫原子主要以C—S、C—SO/C—S—O和SO2-4的形式存在;氮原子的2种存在状态分别是N-6、N-5,表明氮和硫被引入到介孔碳的骨架中。氮原子和硫原子的引入对介孔碳的电化学性能有明显提升。电化学性能测试结果表明,基于水热法合成的氮/硫共掺杂介孔碳复合材料NSMC-4的性能最优,比电容可达到200F/g。杂原子硫和氮作为一种富含电子的活性元素,以表面官能团的形式嵌入到碳骨架中,修饰材料的表面,产生电荷转移动力学以增强材料的电容,合成的氮/硫共掺杂介孔碳复合材料具有作为电极材料的潜力。
The nitrogen/sulfur co-doping mesoporous carbon (NSMC) was synthesized by the hydrothermal method of single thiourea as both sulfur source and nitrogen source,polyether F127 as soft template.Structural characterization shown that N and S were successfully introduced into the carbon atom framework of the mesoporous carbon,where S atoms mainly existed in the form of C—S bonds,C—SO/C—S—O bonds and SO2-4.The N atoms mainly existed in the form of pyrimidine nitrogen and pyrrole nitrogen.The introduction of N and S elements made the mesoporous carbon materials with excellent electrochemical properties.Electrochemical test results shown that NSMC-4 had the best performance with the specific capacitance of 200F/g.Therefore,N and S atoms were embedded in the carbon skeleton in the form of surface functional groups,which can modify the surface of the material to enhance the capacitance of the material.The synthesized NSMC material can be used as promising electrode material.
[1] Sudhan N,Subramani K,Karnan M,et al.Biomass-derived activated porous carbon from rice straw for a high-energy symmetric supercapacitor in aqueous and non-aqueous electrolytes[J].Energy Fuels,2016,31(1):977-985.
[2] 王秀利,何兴权.氮/硫双掺多孔碳负载Fe9S10纳米粒子的氧还原电催化性能[J].高等学校化学学报,2018,39(7):1524-1531.
[3] Volperts A,Dobele G,Zhurinsh A,et al.Wood based activated carbons for supercapacitor electrodes with sulfuric acid electrolyte[J].New Carbon Mater,2017,3(24):319-326.
[4] Ran F,Wu Y,Jiang M,et al.Nanocomposites based on hierarchical porous carbon fiber@vanadium nitride nanoparticles as supercapacitor electrodes[J].Dalton Trans,2018,47:4128-4138.
[5] Chen H,Wei H,Fu N,et al.Nitrogen-doped porous carbon using ZnCl2 as activating agent for high-performance supercapacitor electrode materials[J].J Mater Sci,2018,53:2669-2684.
[6] Seo D H,Yick S,Han Z J,et al.Synergistic fusion of vertical graphene nanosheets and carbon nanotubes for high-perfor-mance supercapacitor electrodes[J].ChemSusChem,2014,7:2317-2324.
[7] 张慧.不同碳材料在双电层超级电容器中的应用研究[D].北京:北京交通大学,2012.
[8] 魏珺谊,高志华,黄伟,等.介孔碳有序度对其负载的CuCoCe催化剂催化合成气制低碳醇性能的影响[J].高等学校化学学报,2018,39(8):1741-1749.
[9] Benzigar M R,Talapaneni S N,Joseph S,et al.Recent advances in functionalized micro and mesoporous carbon materials:synthesis and applications[J].ChemSoc Rev,2018,47(8):2680-2721.
[10] Xu P,Wu Z,Dai W,et al.Synthesis of multiple Ag nanoparticles loaded hollow mesoporous carbon spheres for highly efficient and recyclable catalysis[J].Microporous Mesoporous Mater,2020,314(13):110856.
[11] Zhang M,He L,Shi T,et al.Nanocasting and direct synthesis strategies for mesoporous carbons as supercapacitor electrodes[J].Chem Mater,2018,30:7391-7412.
[12] Paraknowitsch J P,Thomas A.Doping carbons beyond nitrogen:an overview of advanced heteroatom doped carbons with boron,sulphur and phosphorus for energy applications[J].Energy Environ Sci,2013,6(10):2839-2855.
[13] Yan Y,Yin Y X,Xin S,et al.Ionothermal synthesis of sulfur-doped porous carbons hybridized with graphene as superior anode materials for lithium-ion batteries[J].Chem Commun,2012,48(86):10663-10665.
[14] Li W,Yang Z,Li M,et al.Amorphous red phosphorus embedded in highly ordered mesoporous carbon with superior lithium and sodium storage capacity[J].Nano Lett,2016,16(3):1546-1553.
[15] Yang X,Wu D,Chen X,et al.Nitrogen-enriched nanocarbons with a 3-D continuous mesopore structure from polyacrylonitrile for supercapacitor application[J].J Phys Chem C,2010,114(18):8581-8586.
[16] Braghiroli F L,Fierro V,Szczurek A,et al.Hydrothermally treated aminated tannin as precursor of N-doped carbon gels for supercapacitors[J].Carbon,2015,90:63-74.
[17] Lin T,Chen I W,Liu F,et al.Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage[J].Science,2015,350(6267):1508-1513.
[18] Wu F,Li J,Tian Y,et al.3D coral-like nitrogen-sulfur co-doped carbon-sulfur composite for high performance lithium-sulfur batteries[J].Scientific Reports,2015,5:13340.
[19] Seredych M,Jagiello J,Bondose T J.Complexity of CO2 adsorption on nanoporous sulfur-doped carbons-is surface che-mistry an important factor？[J].Carbon,2014,74:207-217.
[20] Hong J,Xia X,Wang Y,et al.Mesoporous carbon nitride with in situ sulfur doping for enhanced photocatalytic hydrogen evolution from water under visible light[J].J Mater Chem,2012,22:15006-15012.
[21] Saha D,Richards C P,Haines R G,et al.Soft-templating of sulfur and iron dual-doped mesoporous carbons:lead adsorption in mixtures[J].Molecule,2020,25(2):403.
[22] Chen F,Zhang M,Ma L,et al.Nitrogen and sulfur codoped micro-mesoporous carbon sheets derived from natural biomass for synergistic removal of chromium(Ⅵ):adsorption behavior and computing mechanism[J].Sci Total Environ,2020,730:138930.
[23] Seredych M,Hulicova-Jurcakova D,Lu G Q,et al.Surface functional groups of carbons and the effects of their chemical character,density and accessibility to ions on electrochemical performance[J].Carbon,2008,46(11):1475-1488.
[24] Fu L,Tang K,Song K,et al.Nitrogen doped porous carbon fibres as anode materials for sodium ion batteries with excellent rate performance[J].Nanoscale,2014,6(3):1384-1389.
[25] 王志广.杂原子掺杂二次电池负极材料的制备及电化学性能研究[D].秦皇岛:燕山大学,2015.
基金资助
青海省应用基础研究项目(2019-ZJ-7013)
PDF
